2-Chloro­pyridine-3-carboxamide

Hua, Y.-P.; Xu, Y.; Wei, X.-H.; Tong, H.-B.

doi:10.1107/S1600536809002256

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o373

doi:10.1107/S1600536809002256

Open

access

2-Chloropyridine-3-carboxamide

Yu-Peng Hua,^a Ying Xu,^a Xue-Hong Wei ^a and Hong-Bo Tong ^a ^*

^aInstitute of Applied Chemistry, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: tong@sxu.edu.cn

(Received 14 January 2009; accepted 17 January 2009; online 23 January 2009)

In the crystal structure of the title compound, C₆H₅ClN₂O, the dihedral angle between the pyridine ring and the carboxamine group is 63.88 (8)°. Intermolecular N—H⋯N and N—H⋯O hydrogen bonds link the molecules into a two-dimensional network.

Related literature

Details of applications of the title compound can be found in: Oda et al. (1993 ); Qin et al. (2001 ).

Experimental

Crystal data

C₆H₅ClN₂O
M_r = 156.57
Monoclinic, P 2₁ /n
a = 6.980 (5) Å
b = 13.627 (9) Å
c = 7.108 (5) Å
β = 91.82 (5)°
V = 675.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.868, T_max = 0.909
2716 measured reflections
1188 independent reflections
1083 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.096
S = 1.11
1188 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.86	2.21	3.003 (3)	154
N2—H2B⋯Oⁱⁱ	0.86	2.17	3.015 (3)	168
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809002256/nc2131sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002256/nc2131Isup2.hkl

checkCIF report

Comment top

The structure of 2-chloropyridine-3-carboxamide has attracted us owing to its fungicidal activities (Oda et al., 1993) and its application in coordination chemistry (Qin et al., 2001). The dihedral angles formed by the pyridine ring and the carboxamine group amount to 63.88 (8)° (Fig. 1). The molecules are connected via intermolecular N—H···N and N—H···O hydrogen bonding into layers, with H···N distances of 2.21 and O···H distances of 2.17 Å (Fig. 2 and Tab. 1).

Related literature top

Related literature on the importance of the title compound can be found in: Oda et al. (1993); Qin et al. (2001).

Experimental top

Ammonia (10 ml, 66 mmol, 25%) was added slowly to a solution of 2-chloropyridine-3-carbonyl chloride (4.0 g, 22 mmol) in THF (20 ml) at 0°C. The reaction mixture was allowed to warm up to room temperature and stirred for 1.5 h. The resulting mixture was dried under vacuum and washed with two 20 ml portions of THF. Then the solution was dried over anhydrous magnesium sulfate. The solvent was removed by vacuum, and the product was collected, yield: 1.93 g, 56%; m.p. 162.5°C. The crystal suitable for X-ray analysis was grown by slow evaporation of the solvent from a diethyl ether solution at 20°. Anal. Calcd for C₆H₅ClN₂O: C, 45.97; H, 3.14; N, 17.82%. Found: C, 46.03; H, 3.22; N, 17.89%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal structure of the title compound along [100] with intermolecular N—H···N and N—H···O hydrogen bonding shown as dashed lines.

2-Chloropyridine-3-carboxamide top

Crystal data top

C₆H₅ClN₂O	F(000) = 320
M_r = 156.57	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.980 (5) Å	Cell parameters from 1764 reflections
b = 13.627 (9) Å	θ = 2.9–26.9°
c = 7.108 (5) Å	µ = 0.49 mm⁻¹
β = 91.82 (5)°	T = 293 K
V = 675.8 (8) Å³	Plate, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	1188 independent reflections
Radiation source: fine-focus sealed tube	1083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −8→6
T_min = 0.868, T_max = 0.909	k = −15→16
2716 measured reflections	l = −6→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0551P)² + 0.1035P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
1188 reflections	Δρ_max = 0.18 e Å⁻³
92 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.051 (8)

Crystal data top

C₆H₅ClN₂O	V = 675.8 (8) Å³
M_r = 156.57	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.980 (5) Å	µ = 0.49 mm⁻¹
b = 13.627 (9) Å	T = 293 K
c = 7.108 (5) Å	0.30 × 0.20 × 0.20 mm
β = 91.82 (5)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1188 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1083 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.909	R_int = 0.021
2716 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.11	Δρ_max = 0.18 e Å⁻³
1188 reflections	Δρ_min = −0.23 e Å⁻³
92 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl	0.14993 (7)	0.10791 (4)	0.88571 (7)	0.0533 (2)
C1	0.3716 (2)	0.07827 (13)	0.7965 (2)	0.0349 (4)
N1	0.4064 (2)	−0.01655 (11)	0.7824 (2)	0.0446 (4)
O	0.5546 (2)	0.30761 (9)	0.8932 (2)	0.0507 (4)
C6	0.4574 (2)	0.25974 (12)	0.7786 (2)	0.0351 (4)
N2	0.3180 (2)	0.29749 (11)	0.6708 (2)	0.0446 (4)
H2A	0.2909	0.3589	0.6786	0.054*
H2B	0.2545	0.2606	0.5930	0.054*
C3	0.6760 (3)	0.12278 (14)	0.6910 (3)	0.0430 (5)
H3	0.7681	0.1692	0.6616	0.052*
C4	0.7153 (3)	0.02376 (16)	0.6735 (3)	0.0505 (5)
H4	0.8331	0.0026	0.6312	0.061*
C2	0.4989 (2)	0.15240 (12)	0.7524 (2)	0.0325 (4)
C5	0.5774 (3)	−0.04231 (14)	0.7198 (3)	0.0506 (6)
H5	0.6042	−0.1088	0.7071	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0357 (3)	0.0599 (4)	0.0647 (4)	−0.0034 (2)	0.0066 (2)	0.0116 (2)
C1	0.0347 (9)	0.0346 (9)	0.0350 (9)	−0.0023 (7)	−0.0060 (7)	0.0017 (7)
N1	0.0541 (10)	0.0302 (8)	0.0485 (9)	−0.0029 (7)	−0.0125 (8)	0.0009 (6)
O	0.0548 (9)	0.0356 (7)	0.0603 (9)	−0.0041 (6)	−0.0181 (7)	−0.0060 (6)
C6	0.0333 (9)	0.0319 (9)	0.0399 (9)	−0.0025 (7)	−0.0003 (7)	0.0020 (7)
N2	0.0456 (9)	0.0300 (8)	0.0573 (10)	0.0039 (6)	−0.0124 (8)	−0.0020 (7)
C3	0.0336 (10)	0.0493 (12)	0.0460 (10)	0.0009 (8)	−0.0022 (8)	−0.0017 (8)
C4	0.0431 (11)	0.0566 (13)	0.0512 (12)	0.0162 (9)	−0.0069 (9)	−0.0109 (9)
C2	0.0298 (9)	0.0335 (9)	0.0337 (9)	0.0002 (7)	−0.0051 (7)	−0.0002 (7)
C5	0.0649 (14)	0.0346 (10)	0.0509 (11)	0.0130 (9)	−0.0191 (10)	−0.0081 (8)

Geometric parameters (Å, º) top

Cl—C1	1.738 (2)	N2—H2B	0.8600
C1—N1	1.319 (2)	C3—C4	1.383 (3)
C1—C2	1.388 (3)	C3—C2	1.385 (3)
N1—C5	1.334 (3)	C3—H3	0.9300
O—C6	1.230 (2)	C4—C5	1.366 (3)
C6—N2	1.324 (2)	C4—H4	0.9300
C6—C2	1.504 (3)	C5—H5	0.9300
N2—H2A	0.8600

N1—C1—C2	125.08 (18)	C4—C3—H3	120.2
N1—C1—Cl	115.07 (14)	C2—C3—H3	120.2
C2—C1—Cl	119.80 (14)	C5—C4—C3	118.6 (2)
C1—N1—C5	116.88 (16)	C5—C4—H4	120.7
O—C6—N2	123.86 (17)	C3—C4—H4	120.7
O—C6—C2	119.55 (15)	C3—C2—C1	116.34 (17)
N2—C6—C2	116.57 (15)	C3—C2—C6	120.00 (16)
C6—N2—H2A	120.0	C1—C2—C6	123.56 (16)
C6—N2—H2B	120.0	N1—C5—C4	123.49 (18)
H2A—N2—H2B	120.0	N1—C5—H5	118.3
C4—C3—C2	119.63 (19)	C4—C5—H5	118.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.86	2.21	3.003 (3)	154
N2—H2B···Oⁱⁱ	0.86	2.17	3.015 (3)	168

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅ClN₂O
M_r	156.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.980 (5), 13.627 (9), 7.108 (5)
β (°)	91.82 (5)
V (Å³)	675.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.868, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	2716, 1188, 1083
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.096, 1.11
No. of reflections	1188
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.86	2.21	3.003 (3)	153.5
N2—H2B···Oⁱⁱ	0.86	2.17	3.015 (3)	168.4

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank the SNSFC (grant No. 2008011021), the Foundation for Returned Overseas Chinese Scholars of Shanxi Province and Shanxi Key Laboratory Foundation for financial support, and the Youth Foundation of Shanxi University, China (grant No. 2006026).

References

Oda, M., Sakaki, T., Sasaki, N., Nonaka, H., Yamagishi, K. & Tomita, H. (1993). J. Pestic. Sci. 18, 49–57. CrossRef Google Scholar
Qin, Z., Jennings, M. C. & Puddephatt, R. J. (2001). Inorg. Chem. 40, 6220–6228. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison Wisconsin, USA. Google Scholar